Excitons Diffusion, Energy Transfer

Wannier exciton Charge-transfer exciton Frenkel exciton Exciton Diffusion Exciton Energy Transfer (Frster, Dexter)

Handout: Haskal et al., Phys. Rev. B 59, 4449 (1995). Acknowledgment:

figures in slides 4-6 are from Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg

@ MIT

February 26, 2002 Organic Optoelectronics - Lecture 7

Absorption of Light

d I0 I

Lambert-Beer Law

I = I0 e-Cd

absorption coefficient of the molecules d - thickness of a homogeneous sample C - concentration

Wannier exciton
(typical of inorganic semiconductors)

Excitons
(bound electron-hole pairs)
treat excitons as chargeless particles capable of diffusion,

Frenkel exciton
(typical of organic materials)

SEMICONDUCTOR PICTURE
CONDUCTION BAND

also view them as excited states of the molecule

MOLECULAR PICTURE
S1

S0
VALENCE BAND

GROUND STATE

WANNIER EXCITON

binding energy ~10meV radius ~100

Charge Transfer (CT) Exciton

(typical of organic materials)

GROUND STATE

FRENKEL EXCITON

binding energy ~1eV radius ~10

Wannier-Mott Excitons

Coulombic interaction between the hole and the electron is given by EEX = -e2/r The exciton energy is then E = EION EEX/n2 , n = 1,2, EION energy required to ionize the molecule n exciton energy level EEX = 13.6 eV /m reduced mass = memh / (me+mh)

An Example of Wannier-Mott Excitons

exciton progression fits the expression [cm-1] = 17,508 800/n2 corresponding to = 0.7 and = 10

Charge Transfer Excitons

Solution Absorption
PTCDA in DMSO
6
AGGREGATE State

2 M 1.6 M . . . 0.25 M

Absorption [a.u.]

AGGREGATE STATE ABSORPTION increases with PTCDA solution concentration

1.8

2.0

2.2

2.4

2.6

2.8

3.0

Energy [eV]

PTCDA Thin Film

CT [ST-2]

CT [0-F]

S1 [0-0] S1 [0-1]

S1 [0-2]

Fluorescence
CT [ST-3]

S1 [0-3]

1.5

CT [ST-1]

2.0

CT [0-ST]

Absorption

2.5 Energy [eV]

3.0

3.5

PTCDA Solution
(~ 2M in DMSO)
0.6 eV

PTCDA Thin Film

Fluorescence

Absorption

1.5

2.0

2.5 Energy [eV]

3.0

3.5

Exciton Quantum Confinement in Multi Quantum Wells

So and Forrest, Phys. Rev. Lett. 66, 2649 (1991). Shen and Forrest, Phys. Rev. B 55, 10578 (1997).

Exciton radius = 13

mh, = 0.18 mo
30

E LUMO

E 1s [meV]

20

mh, = 0.16 mo mh, = 0.14 mo

E HOMO d

NTCDA

NTCDA

PTCDA

PTCDA

0 10 100 1000

d []

PTCDA

10

(a) Delocalized CT Exciton

Bandwidth >> VPSEUDO

(b)

Localized CT Exciton
Bandwidth << VPSEUDO

r
V [eV]

r
-1

V [eV]

-1

-2

-2

-3

-3

Electronic Processes in Molecules

density of available S and T states on surrounding molecules
JABLONSKI DIAGRAM

10 ps
INTERNAL CONVERSION
INTERSYSTEM CROSSING

Energy

FRSTER, DEXTER or RADIATIVE ENERGY TRANSFER

S: spin=0 (singlet) states T: spin=1 (triplet) states

PHOSPHORESCENCE

S1
ABSORPTION

1-10 ns
T1
FLUORESCENCE

>100 ns

S0

Effect of Dopants on the Luminescence Spectrum

1.0 Normalized EL Intensity 0.8 0.6 0.4 0.2 0.0 400 500 600
Al N O

N O

Alq3

DCM2:Alq3 PtOEP:Alq3 3
N N Pt N N

NC

CN

700

800

Wavelength [nm]

Nonradiative Energy Transfer

dopant molecules (generate luminescence) host molecules

How does an exciton in the host transfer to the dopant?

Two possible energy transfer processes: 1. Frster transfer 2. Dexter transfer

Frster transfer - resonant dipole-dipole coupling - donor and acceptor transitions must be allowed very fast <10-9s

RO <

100

Acceptor (dye) Donor

Donor* Acceptor

Donor Acceptor*

only singlet excitons participate

Frster transfer - Example

Alq3 (DONOR)

Alq3 LUMO

DCM LUMO

ABSORPTION

PL

200 300 400 500 600 700 800 900 Wavelength [nm]

FRSTER ENERGY TRANSFER DCM HOMO

DCM
ABSORPTION

(ACCEPTOR)
EL

Alq3 HOMO

DCM2 in Alq3 Alq3 low DCM2 high DCM2

200 300 400 500 600 700 800 900 Wavelength [nm]

for efficient transfer donor emission and acceptor absorption must overlap

Frster transfer Rate Equations 2 2 2 (E) Pda = | Z E )g FA dE ( E )dE KET = (2/) |<D,A*|HDA |D*,A> a(E) fgdD(
Energy transfer rate (KET) depends on the overlap integral
FOR DIPOLEDIPOLE-DIPOLE INTERACTION: 6 1 R0 K ET ( R ) =

ALLOWED TRANSITIONS:
1D* 1D* + 1A 1D + 1A* + 3A(Tn) 1D + 3A*(Tm)

gA(E)

gD(E)

= donor (D) (from Blasse & Grabmaier)

Dexter transfer diffusion of excitons from donor to acceptor

Wigner-Witmer spin conservation rules A+BC+D total spin of reactants: (SA+SB),(SA+SB-1),....,|SA-SB| total spin of products: (SC+SD),(SC+SD-1),....,|SC-SD| reaction allowed if two sequences have a number in common

only singlet-singlet, triplet-triplet allowed speed?

Acceptor ( eg. phosphorescent dye )

Donor

Donor* Acceptor

Donor Acceptor*

~ 10

Nonradiative Energy Transfer

Frster, Coulombic
(long range ~30-100 )

Dexter, e- exchange
(short range ~6-20 )

D*
SINGLET-SINGLET TRANSFER ONLY

D*

A
SINGLET-SINGLET & TRIPLET-TRIPLET TRANSFER

A*

Diffusion of Excitons
If energy transfer occurs between the donor and acceptor molecules of the same species, the term energy migration is used.
Alq3 exciton diffusion length ~ 10 nm

40

PL Internal Efficiency [%]

30

20

10

PL efficiency of Alq3 on glass

0.01 0.1 1

Film Thickness [m]

The four general methods used to measure diffusion of excitons are: bulk quenching, surface quenching, bimolecular recombination, and photoconduction